Electrochemical removal of amphoteric ions

Abstract

Significance Water treatment is required for a sustainable potable water supply and can be leveraged to harvest valuable elements. Crucial to these processes is the removal of charge pH-dependent species from polluted water, such as boron, ammonia, and phosphate. These species can be challenging for conventional technologies. Currently, boron removal requires several reverse-osmosis stages, combined with dosing a caustic agent. Capacitive deionization (CDI) promises to enable effective removal of such species without chemical additives but requires a deep understanding of the coupled interplay of pH dynamics, ion electrosorption, and transport phenomena. Here, we provide a detailed theory tackling this topic and show both theoretically and experimentally highly counterintuitive design rules governing pH-dependent ion removal by CDI. Several harmful or valuable ionic species present in seawater, brackish water, and wastewater are amphoteric, weak acids or weak bases, and, thus, their properties depend on local water pH. Effective removal of these species can be challenging for conventional membrane technologies, necessitating chemical dosing of the feedwater to adjust pH. A prominent example is boron, which is considered toxic in high concentrations and often requires additional membrane passes to remove during seawater desalination. Capacitive deionization (CDI) is an emerging membraneless technique for water treatment and desalination, based on electrosorption of salt ions into charging microporous electrodes. CDI cells show strong internally generated pH variations during operation, and, thus, CDI can potentially remove pH-dependent species without chemical dosing. However, development of this technique is inhibited by the complexities inherent to the coupling of pH dynamics and ion properties in a charging CDI cell. Here, we present a theoretical framework predicting the electrosorption of pH-dependent species in flow-through electrode CDI cells. We demonstrate that such a model enables insight into factors affecting species electrosorption and conclude that important design rules for such systems are highly counterintuitive. For example, we show both theoretically and experimentally that for boron removal, the anode should be placed upstream and the cathode downstream, an electrode order that runs counter to the accepted wisdom in the CDI field. Overall, we show that to achieve target separations relying on coupled, complex phenomena, such as in the removal of amphoteric species, a theoretical CDI model is essential.